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"[…] a fascinating and well-written evaluation of the present prestige of our wisdom of the composition of the center surroundings and the fundamental radiative, dynamical and photochemical methods which retain it. " (Bulletin American Meteorological Society)
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Extra resources for Aeronomy of the Middle Atmosphere: Chemistry and Physics of the Stratosphere and Mesosphere (Atmospheric and Oceanographic Sciences Library)
One simple explanation for this is that only certain orientations are conducive to reactions, especially for complex molecules. Thus we can introduce a “steric factor” to represent the probability that the molecules will be in the proper geometric arrangement when they collide. Finally, another area of possible failure in the hard sphere model lies in the true nature of the approaching particles: They are not hard spheres, rather, they exert attractive forces on one another. In the case of ion-molecule reactions, the attractive forces are coulombic, and exert an inﬂuence even at relatively large distances.
Note the very long radiative lifetimes of O (1 D), O2 (1 ∆g ), and N (2 D). Transitions of these species to their respective ground states involve violation of the spin conservation rule, and are therefore relatively slow. The O (1 S) → O (1 D) transition, which produces the green line, is spin allowed, but corresponds to ∆L of 2, and is therefore somewhat unfavorable. In contrast, the NO (A2 Σ+ ) → NO (X2 Π) transition is fully allowed and the radiative lifetime of this state is correspondingly short.
9. Potential energy curves for a predissociative process in a diatomic molecule. 7, can such a transition lead to dissociation? Dissociation can often occur in such a case through curve crossing onto a predissociating state. 9 presents a corresponding potential energy curve showing this phenomenon. The excited state, XY∗ , which is initially produced, can cross into XY∗∗ by a non-radiative transition or by collisioninduced crossing. From the predissociating state, ground state atoms are eventually produced.